JP7003659B2 - Resin composition - Google Patents

Description

The present invention relates to a resin composition suitably used for a surface protective film of a semiconductor element or the like, an interlayer insulating film, an insulating layer of an organic electroluminescent element, or the like.

Conventionally, the surface protective film and interlayer insulating film of semiconductor devices, the insulating layer of organic electrolytic devices, and the flattening film of TFT substrates have been made of polyimide resins and polybenzoxazoles with excellent heat resistance, electrical insulation, and mechanical properties. Resin was widely used.

When the coating film of the polyimide precursor, the polybenzoxazole precursor, or the polyamide-imide precursor is thermally dehydrated and closed to obtain a thin film having excellent heat resistance and mechanical properties, high-temperature firing at about 350 ° C. is usually required. In addition, the operation for obtaining a thin film having excellent heat resistance and mechanical properties by thermally dehydrating and closing the coating film of the polyimide precursor, the polybenzoxazole precursor, and the polyamide-imide precursor is fired, and the change of the coating film is cured. May be called. However, memory devices used in recent years and mold resins used when manufacturing semiconductor packages are vulnerable to high-temperature processes, and from the viewpoint of semiconductor package reliability, surface protective films and interlayer insulating films have a temperature of 250 ° C or less. More preferably, a polyimide-based resin, a polybenzoxazole-based resin, and a polyamide-imide-based resin, which can be cured by firing at a low temperature of 220 ° C. or lower and have higher mechanical and thermal properties, are required.

Examples of the resin composition that can be cured at a low temperature include a resin composition containing a resin such as polyimide, polybenzoxazole, polybenzoimidazole, and polybenzothiazole, and a thermal cross-linking agent (Patent Document 1), an alkali-soluble polyamide-imide, and light. Positive type containing an acid generator, a solvent and a cross-linking agent, a positive photosensitive polyamide-imide resin composition (Patent Document 2), an alkali-soluble polyimide, a quinonediazide compound, a thermal cross-linking agent, a thermal acid generator and an adhesion improver. A photosensitive polyimide resin composition (Patent Document 3) and the like are known.

Japanese Unexamined Patent Publication No. 2007-16214 Japanese Unexamined Patent Publication No. 2007-240554 Japanese Unexamined Patent Publication No. 2013-72935

However, the resin compositions that can be cured by heat treatment at a low temperature of 250 ° C. or lower, as disclosed in Patent Documents 1 to 3, have problems in terms of properties such as heat resistance and chemical resistance.

The present invention solves the above-mentioned problems associated with the prior art, and can obtain a cured film having excellent heat resistance, chemical resistance, and elongation at break while being curable by heat treatment at a low temperature. It is an object of the present invention to provide a resin composition.

（一般式（１）中、ＸおよびＹは、それぞれ独立に２個以上の炭素原子を有する２～８価の有機基を表す。Ｒ ^１ およびＲ ^２ は、それぞれ独立に水素、または炭素数１～２０の有機基を表す。ｎは１０～１００，０００の範囲内の整数を示す。ｒおよびｓは０～２の範囲内の整数、ｐおよびｑは０～４の範囲内の整数を表す。）

（一般式（２）中、Ｒ ^３ ～Ｒ ^６ はそれぞれ独立に炭素数１～６のアルキレン基を表す。Ｒ ^７ ～Ｒ ^１４ はそれぞれ独立に水素、フッ素、または炭素数１～６のアルキル基を表す。但し、括弧内に表される構造はそれぞれ異なる。ｘ、ｙ、ｚはそれぞれ独立に０～３５の整数を表す。） (A) Alkaline-soluble, comprising one or more selected from polybenzoxazole precursors, polyimide precursors, polyamide-imide precursors, and copolymers thereof, and having a benzoxazole precursor structure and an aliphatic group. Resin, as well as
It is a resin composition containing (B) a thermal acid generator and (E) an antioxidant.
An alkali comprising (A) one or more selected from the polybenzoxazole precursor, the polyimide precursor, the polyamide-imide precursor, and a copolymer thereof, and having a benzoxazole precursor structure and an aliphatic group. Soluble resin,
It has a structural unit represented by the general formula (1) and has a structural unit.
It is preferable that Y in the general formula (1) is the resin composition according to claim 2, which has an aliphatic group represented by the following general formula (2).

(In the general formula (1), X and Y each independently represent a 2- to 8-valent organic group having two or more carbon atoms. R ¹ and R ² are independently hydrogen or 1 carbon atom, respectively. Represents an organic group of ~ 20; n represents an integer in the range of 10-100,000; r and s represent an integer in the range of 0-2, p and q represent an integer in the range of 0-4. .)

(In the general formula (2), R ³ to R ⁶ independently represent an alkylene group having 1 to 6 carbon atoms, and R ⁷ to R ¹⁴ independently represent hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms, respectively. However, the structures represented in parentheses are different. X, y, and z each independently represent an integer of 0 to 35.)

According to the resin composition of the present invention, a cured film having excellent heat resistance, chemical resistance, and elongation at break can be obtained while being curable by heat treatment at a low temperature.

It is a figure which showed the enlarged cross section of the pad part of the semiconductor device which has a bump. It is a figure which showed the detailed manufacturing method of the semiconductor device which has a bump. It is sectional drawing of the manufacturing process of the semiconductor device which shows the Example of this invention. It is sectional drawing of the coil component of the inductor device which shows the Example of this invention.

The resin composition of the present invention comprises one or more selected from (A) a polybenzoxazole precursor, a polyimide precursor, a polyamide-imide precursor, and a copolymer thereof, and has a benzoxazole precursor structure. And an alkali-soluble resin having an aliphatic group, and a resin composition containing (B) a heat acid generator and (E) an antioxidant. Further, it is preferable that the resin composition further contains (C) a heat-crosslinking agent and (D) a photosensitive compound. Hereinafter, they may be abbreviated as the component (A), the component (B), the component (C), and the compound (D), respectively.

In the present invention, alkali-soluble means a prebaked film formed by the following method.
It means that the dissolution rate when immersed in the alkaline aqueous solution described below is 50 nm / min or more. Specifically, a solution in which a resin is dissolved in γ-butyrolactone is applied onto a silicon wafer and prebaked at 120 ° C. for 4 minutes to form a prebake film having a film thickness of 10 μm ± 0.5 μm, and the prebake film is formed by 23 ±. It means that the dissolution rate obtained from the decrease in film thickness when the film is immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution at 1 ° C. for 1 minute and then rinsed with pure water is 50 nm / min or more.

The alkali-soluble resin which is the component (A) used in the present invention preferably has an acidic group in the structural unit of the resin and / or at the end of the main chain. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, a sulfonic acid group and a thiol group. Having such an acidic group can have good alkali solubility. The content of the acidic group in the component (A) is preferably 1% by mass or more from the viewpoint of improving alkali solubility, and preferably 30% by mass or less from the viewpoint of chemical resistance, water absorption and the like.

The component (A) preferably has a fluorine atom. Since the component (A) has a fluorine atom, the formed film has water repellency, and when the film is developed with an alkaline aqueous solution, the penetration of the alkaline aqueous solution into the interface between the film and the substrate is suppressed. The alkaline aqueous solution used for development may be referred to as an alkaline developer. The fluorine atom content in the component (A) is preferably 5% by mass or more from the viewpoint of the effect of suppressing the penetration of the alkaline aqueous solution into the interface between the membrane and the substrate, and 20% by mass from the viewpoint of solubility in the alkaline aqueous solution. The following is preferable.

The alkali-soluble resin as the component (A) preferably has high heat resistance. In particular, since excellent properties can be obtained as a flattening film, an insulating layer, a partition wall, a protective film, and an interlayer insulating film used in organic light emitting devices, display devices, and semiconductor devices, they are subjected to temperature conditions of 160 ° C. or higher after heat treatment. Those with a small amount of outgas are preferable. Specifically, polybenzoxazole precursors, polyimide precursors, polyamideimide precursors, and copolymers thereof are given as preferable examples.

The component (A) used in the present invention preferably has a structural unit represented by the following general formula (1). Moreover, it may have other structural units further. Examples of other structural units in such a case include, but are limited to, a structure having a skeleton in which two cyclic structures are bonded to a quaternary carbon atom constituting an imide structure or a cyclic structure, a siloxane structure, and the like. Not done. When further having other structural units, it is preferable to have 50 mol% or more of the structural units represented by the general formula (1) out of the total number of structural units.

(In the general formula (1), X and Y each independently represent a 2- to 8-valent organic group having two or more carbon atoms. R ¹ and R ² are independently hydrogen or 1 carbon atom, respectively. Represents an organic group of ~ 20; n represents an integer in the range of 10-100,000; r and s represent an integer in the range of 0-2, p and q represent an integer in the range of 0-4. .)
In addition, the component (A) has a benzoxazole precursor structure. By having the benzoxazole precursor structure, the photosensitive performance is improved, and high elongation can be imparted to the cured film obtained by curing the resin composition containing the component (A), and further, the benzoxazole precursor can be used. By closing the ring, heat resistance and chemical resistance are improved.

In addition, the component (A) has an aliphatic group. The aliphatic group preferably has at least one organic group of an alkylene group and an oxyalkylene group. Specific examples thereof include an alkylene group, a cycloalkylene group, an oxyalkylene group and an oxycycloalkylene group. Further, the aliphatic group is preferably represented by the following general formula (2).

(In the general formula (2), R ³ to R ⁶ independently represent an alkylene group having 1 to 6 carbon atoms, and R ⁷ to R ¹⁴ independently represent hydrogen, fluorine, or an alkyl having 1 to 6 carbon atoms, respectively. Represents a group. However, the structures represented in parentheses are different. X, y, and z each independently represent an integer of 0 to 35.)
Since the component (A) has an aliphatic group, the cured film obtained by curing the resin composition containing the component (A) has high elongation. Further, since the component (A) has an aliphatic group, the resin becomes flexible, and an increase in stress generated when the benzoxazole precursor structure of the resin is closed can be suppressed. Therefore, it is possible to suppress an increase in stress on the substrate wafer due to dehydration ring closure of the benzoxazole precursor structure. In addition, since the aliphatic group has low ultraviolet absorption, its introduction improves i-ray transparency and can realize high sensitivity at the same time.

The weight average molecular weight of the component (A) used in the present invention is preferably 600 or more, and more preferably 900 or more, in that the cured film has high elongation. Further, in terms of maintaining the solubility in an alkaline solution, it is preferably 2,000 or less, more preferably 1,800 or less, and even more preferably 1,500 or less.

In the present invention, the weight average molecular weight (Mw) can be confirmed by using GPC (gel permeation chromatography). For example, it can be measured by using N-methyl-2-pyrrolidone (hereinafter, may be abbreviated as NMP) as a developing solvent and calculated in terms of polystyrene.

The component (A) used in the present invention preferably has a structural unit represented by the general formula (1). In the general formula (1), (OH) _p -X- (COOR ¹ ) _r represents an acid residue. X is a divalent to octavalent organic group having two or more carbon atoms, and more preferably an organic group having an aromatic ring or an aliphatic group and having 5 to 40 carbon atoms.

Examples of the acid component include terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, bis (carboxyphenyl) hexafluoropropane, biphenyldicarboxylic acid, benzophenone dicarboxylic acid, and triphenyldicarboxylic acid as examples of dicarboxylic acids. Examples of tetracarboxylic acids such as acids, trimesic acid, diphenyl ether tricarboxylic acid, biphenyl tricarboxylic acid are pyromellitic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyl. Tetracarboxylic acid, 2,2', 3,3'-biphenyltetracarboxylic acid, 3,3', 4,4'-diphenyl ether tetracarboxylic acid, 3,3', 4,4'-benzophenone tetracarboxylic acid, 2 , 2', 3,3'-benzophenone tetracarboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) propane, 2,2-bis (2,3-dicarboxyphenyl) propane, 1,1- Bis (3,4-dicarboxyphenyl) ethane, 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) Methan, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetracarboxylic acid, 9,9-bis (3,4-dicarboxyphenyl) fluorene, 9,9-bis {4 -(3,4-Dicarboxyphenoxy) phenyl} fluorene, 2,3,6,7-naphthalenetetracarboxylic acid, 2,3,5,6-pyridinetetracarboxylic acid, 3,4,9,10-perylenetetra Carboxylic acid, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane and aromatic tetracarboxylic acid having the structure shown below, butanetetracarboxylic acid, cyclobutanetetracarboxylic acid, 1,2,3 Examples include, but are not limited to, aliphatic tetracarboxylic acids such as 4-cyclopentanetetracarboxylic acid. Two or more of these may be used.

R ¹⁵ represents an oxygen atom, C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ . R ¹⁶ and R ¹⁷ represent a hydrogen atom or a hydroxyl group.

These acids can be used as is or as acid anhydrides, halides and active esters.

Further, (OH) _q −Y− (COOR ² ) _s in the general formula (1) represents a residue of diamine. Y is a divalent to octavalent organic group having two or more carbon atoms, and more preferably an organic group having 5 to 40 carbon atoms containing an aromatic ring or an aliphatic group described later.

Specific examples of the diamine used as the component (A) include 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1, 4-bis (4-aminophenoxy) benzene, benzidine, m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis (4-aminophenoxy) biphenyl, bis {4- (4-Aminophenoxy) phenyl} ether, 1,4-bis (4-aminophenoxy) benzene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'- Diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-diethyl-4,4'-diaminobiphenyl, 2,2', 3,3'-tetramethyl-4,4' -Diaminobiphenyl, 3,3', 4,4'-tetramethyl-4,4'-diaminobiphenyl, 2,2'-di (trifluoromethyl) -4,4'-diaminobiphenyl, 9,9-bis (4-Aminophenyl) fluorene, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane or compounds in which at least part of the hydrogen atoms of these aromatic rings are replaced with alkyl or halogen atoms. , An aliphatic cyclohexyldiamine, methylenebiscyclohexylamine and diamines having the structures shown below, but are not limited thereto. Two or more of these may be used.

R ¹⁵ represents an oxygen atom, C (CF ₃ ) ₂ , or C (CH ₃ ) ₂ . R ¹⁶ to R ¹⁹ independently represent a hydrogen atom or a hydroxyl group, respectively.

These can be used as diamines or as the corresponding diisocyanate compounds, trimethylsilylated diamines.

The component (A) used in the present invention has an aliphatic group. And it is preferable that Y in the general formula (1) has an aliphatic group. Further, it is more preferable that the aliphatic group is an aliphatic group represented by the general formula (2).

By having an aliphatic group on the Y, that is, the diamine side in the general formula (1), high elongation and low stress can be obtained in the cured film, and the resin composition of the present invention can be made highly sensitive. Further, when Y in the general formula (1) has an aliphatic group represented by the general formula (2), the adhesion of the substrate to the metal (for example, copper) can be improved. Specifically, since an interaction such as a coordination bond can be obtained between the ether group contained in the general formula (2) and the metal, high adhesion of the substrate to the metal can be obtained.

Specific examples of the diamine having an aliphatic group include ethylenediamine, 1,3-diaminopropane, 2-methyl-1,3-propanediamine, 1,4-diaminobutane, 1,5-diaminopentane, and 2-methyl-. 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1, 12-Diaminododecane, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,2-bis (aminomethyl) cyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1, 4-bis (aminomethyl) cyclohexane, 4,4'-methylenebis (cyclohexylamine), 4,4'-methylenebis (2-methylcyclohexylamine), KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP- 409, RP-2005, RP-2009, RT-1000, HE-1000, HT-1100, HT-1700, and the like (these trade names are manufactured by HUNTSMAN Co., Ltd.) and the like can be mentioned. In addition, -S-, -SO-, -SO _2- , -NH-, -NCH _3- , -N (CH ₂ CH ₃ )-, -N (CH ₂ CH ₂ CH ₃ )-, -N (CH) (CH ₃ ) ₂ )-, -COO-, -CONH-, -OCONH-, -NHCONH- may be included. Among these, a diamine having an aliphatic group represented by the general formula (2) is preferable, and for example, KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D. -200, D-400, D-2000, THF-100, THF-140, THF-170, RE-600, RE-900, RE-2000, RP-405, RP-409, RP-2005, RP-2009 , RT-1000, HE-1000, HT-1100, HT-1700, (above, trade name, manufactured by HUNTSMAN Co., Ltd.) and the like are preferable.

The aliphatic group is preferably contained in the total diamine residue in an amount of 5 to 40 mol%, more preferably 10 to 30 mol%. By including the aliphatic group in this range, the developability when developing with an alkaline aqueous solution is enhanced, and the elongation of the cured film obtained by heating is improved.

Further, the component (A) used in the present invention may contain an aliphatic group having a siloxane structure as long as the heat resistance is not deteriorated, whereby the adhesiveness to the substrate can be improved. Specific examples of the diamine component include those obtained by copolymerizing 1 to 15 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like. .. When it is contained in an amount of 1 mol% or more, it is preferable in terms of improving the adhesiveness to a substrate such as a silicon wafer, and when it is 15 mol% or less, it is preferable in that it does not reduce the solubility in an alkaline solution.

Further, the alkali-soluble resin as the component (A) is preferably a resin having an acidic group at the end of the main chain. Such a resin can be obtained by sealing the end of the alkali-soluble resin with a monoamine having an acidic group, an acid anhydride, an acid chloride, or a monocarboxylic acid.

Preferred examples of monoamines that can be used to obtain an alkali-soluble resin having an acidic group at the end of the main chain are 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, and 1-hydroxy-6-aminonaphthalene. , 1-Hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy- 7-Aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-Aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3 -Aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol and the like can be mentioned. Two or more of these may be used.

In addition, preferred examples of acid anhydrides, acid chlorides and monocarboxylic acids that can be used to obtain an alkali-soluble resin having an acidic group at the end of the main chain are phthalic acid anhydride, maleic anhydride, nadic acid anhydride and cyclohexanedicarboxylic acid. Acid anhydrides, acid anhydrides such as 3-hydroxyphthalic acid anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1- Monocarboxylic acids such as hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, and these. Monoacid chloride compound in which the carboxyl group of the above is acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, A monoacid chloride compound in which only one carboxyl group of dicarboxylic acids such as 2,6-dicarboxynaphthalene is acid chlorided, a monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3- Examples thereof include active ester compounds obtained by reaction with dicarboxyimide. Two or more of these may be used.

The content of the acidic group at the end of the main chain of the alkali-soluble resin derived from the terminal encapsulant such as monoamine, acid anhydride, acid chloride, and monocarboxylic acid is 100 mol% in total of the acid and amine components constituting the resin. 2 to 25 mol% is preferable.

When the alkali-soluble resin as the component (A) is a resin having an acidic group at the end of the main chain, the acidic group at the end of the main chain of the component (A) can be easily detected by the following method. For example, a resin having an acidic group at the end of the main chain is dissolved in an acidic solution, decomposed into an amine component and an acid component, which are constituent units of the resin, and this is measured by gas chromatography (GC) or NMR. The terminal encapsulant that is the source of the acidic group can be easily detected. Apart from this, it is possible to detect a resin having an acidic group at the end of the main chain by directly measuring a pyrolysis gas chromatograph (PGC), an infrared spectrum and a ¹³ C-NMR spectrum.

Further, in the cured film obtained by curing the resin composition of the present invention, the proportion of the benzoxazole precursor structure closed to polybenzoxazole is preferably 30% or more due to the action of the component (B) described later. When the ring is closed by 30% or more, a cured film having a small amount of outgas, high heat resistance, high chemical resistance, and high elongation at break can be obtained.

The solvent used for polymerizing the alkali-soluble resin which is the component (A) used in the present invention (hereinafter referred to as a polymerization solvent) may be any solution as long as it can dissolve tetracarboxylic acid dianhydrides and diamines which are raw material monomers. The type is not particularly limited. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N'-dimethylpropylene urea, N, N-dimethyliso. Cyclic esters such as butyric acid amide, methoxy-N, N-dimethylpropionamide amides, γ-butyrolactone, γ-valerolactone, δ-valerolactone, γ-caprolactone, ε-caprolactone, α-methyl-γ-butyrolactone , Ester carbonates, carbonates such as propylene carbonate, glycols such as triethylene glycol, phenols such as m-cresol and p-cresol, acetophenone, 1,3-dimethyl-2-imidazolidinone, sulfolane, dimethyl sulfoxide, etc. Can be mentioned.

In order to dissolve the component (A) after the reaction, the polymerization solvent is preferably used in an amount of 100 parts by mass or more, more preferably 150 parts by mass or more, based on 100 parts by mass of the obtained component (A). It is preferable to use 1,900 parts by mass or less, and more preferably 950 parts by mass or less in order to obtain the resin as a powder at the time of precipitation recovery.

The component (A) having the structural unit represented by the general formula (1) in the present invention preferably has a weight average molecular weight of 10,000 or more and 50,000 or less. When the weight average molecular weight is 10,000 or more, it is preferable because the mechanical properties after curing can be improved, and more preferably 20,000 or more. On the other hand, when the weight average molecular weight is 50,000 or less, the developability with an alkaline aqueous solution can be improved, which is preferable.

When two or more kinds of alkali-soluble polyimide precursors, polybenzoxazole precursors, polyamideimide precursors or copolymers thereof are contained, the weight average molecular weight of at least one kind may be within the above range.

The component (A) used in the present invention can be produced by a known method.

The polybenzoxazole precursor used in the present invention is composed of a benzoxazole precursor, and can be obtained, for example, by subjecting a bisaminophenol compound and a dicarboxylic acid to a condensation reaction. Specifically, a method of reacting a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) with an acid and adding a bisaminophenol compound thereto, or a dicarboxylic acid in a solution of a bisaminophenol compound to which a tertiary amine such as pyridine is added. For example, a solution of dichloride is dropped. Further, it may have an imide precursor structure or an imide structure, and in that case, the content ratio of the imide precursor structure in the polybenzoxazole precursor or the content ratio of the benzoxazole precursor structure when the imide structure is 100 parts by mass. Is preferably 101 to 10000 parts by mass.

As a method for producing the polyimide precursor used in the present invention, for example, a method of reacting a tetracarboxylic acid dianhydride with a diamine compound at a low temperature, a diester is obtained with a tetracarboxylic acid dianhydride and an alcohol, and then an amine is used. It can be synthesized by a method of reacting in the presence of a condensing agent, a method of obtaining a diester by tetracarboxylic acid dianhydride and an alcohol, and then acid chlorideizing the remaining dicarboxylic acid and reacting with an amine. When having a benzoxazole precursor structure, the benzoxazole precursor structure is introduced into the polyimide precursor by using a diamine having the benzoxazole precursor in advance or by applying the method for producing the polybenzoxazole precursor. Can be done. In that case, when the imide precursor structure in the polyimide precursor is 100 parts by mass, the content ratio of the benzoxazole precursor structure is preferably 1 to 99 parts by mass.

As a method for producing a polyamideimide precursor used in the present invention, for example, tricarboxylic acid is first made into an acid anhydride, and the remaining carboxylic acid is reacted with an acid chloride or a dehydration condensing agent such as dicyclohexylcarbodiimide (DCC) to form an amine. It can be synthesized by a reaction method or the like. When having a benzoxazole precursor structure, the benzoxazole precursor structure is introduced into the polyamideimide precursor by using a diamine having the benzoxazole precursor in advance or by applying the method for producing the polybenzoxazole precursor. be able to. In that case, when the imide precursor structure in the polyamide-imide precursor is 100 parts by mass, the content ratio of the benzoxazole precursor structure is preferably 50 to 10,000 parts by mass.

In the present invention, other alkali-soluble resin may be contained in addition to the component (A). Specific examples thereof include polyimide, polybenzoxazole, phenol resin, a polymer containing a radically polymerizable monomer having an alkali-soluble group, a siloxane polymer, a cyclic olefin polymer, and a cardo resin. These resins may be used alone or in combination of a plurality of resins. In that case, when the total of the component (A) and the other alkali-soluble resin is 100 parts by mass, the content ratio of the other alkali-soluble resin is preferably 1 to 50 parts by mass.

The resin composition of the present invention contains (B) a thermoacid generator. The (B) thermal acid generator used in the present invention generates an acid by heat treatment after development and acts as a catalyst for promoting the cyclization of the imide precursor and the benzoxazole precursor of the component (A). The chemical reaction can proceed at a lower temperature. Further, when the resin composition of the present invention is a resin composition further containing (C) a heat-crosslinking agent described later, a catalyst that promotes a cross-linking reaction between the resin of the component (A) and (C) the heat-crosslinking agent. Also works as. Therefore, by containing (B) a thermal acid generator, the denseness of the cured film after curing is improved, and as a result, heat resistance and chemical resistance are improved.

It is more preferable that the thermal acid generator (B) used in the present invention has a thermal decomposition start temperature of 140 ° C. or higher. Further, the thermal decomposition start temperature is preferably 220 ° C. or lower, more preferably 200 ° C. or lower. The thermal decomposition start temperature referred to here means a boiling point or a decomposition temperature, and the decomposition temperature is a temperature at which thermal decomposition starts before reaching the melting point.

Further, no acid is generated when the resin composition of the present invention is applied to a substrate and then dried (pre-bak: 70 ° C to 140 ° C), and heat-cured (cure: 140 to 220) after patterning in subsequent exposure and development. It is preferable to select a substance that generates an acid at ° C.) because the decrease in sensitivity during development can be suppressed and the curing temperature can be lowered, so that the stress increase of the substrate due to high-temperature heating can be suppressed. Therefore, the thermal acid generator (B) used in the present invention preferably has a thermal decomposition start temperature of 140 to 220 ° C., and more preferably 140 to 200 ° C.

(B) Examples of the thermal acid generator include a sulfonic acid ester compound and an onium salt such as a sulfonium salt.

The acid generated from the thermal acid generator has an acid dissociation constant of 2.0 from the viewpoint of its function as a catalyst for promoting the cyclization and the cross-linking reaction of the imide precursor and the benzoxazole precursor of the component (A). The following strong acids are preferred.

As the acid generated by thermal decomposition, sulfonic acid, boric acid and the like are preferable.

Examples of the sulfonic acid include aryl sulfonic acids such as p-toluene sulfonic acid and benzene sulfonic acid, alkyl sulfonic acids such as methane sulfonic acid, ethane sulfonic acid, butane sulfonic acid and camphor sulfonic acid, and haloalkyl sulfonic acids such as trifluoromethane sulfonic acid. Acids and the like are preferred.

As the boric acid, for example, tetrafluoroboric acid, tetrakis (pentafluorophenyl) boric acid and the like are preferable.

The component (B) used in the present invention is one or more selected from a sulfonic acid ester compound represented by the general formula (3), a sulfonic acid ester compound represented by the general formula (4), and an onium salt. It is preferably a compound.

(In the general formulas (3) and (4), R ²⁰ to R ²² independently represent an aliphatic group having 1 to 12 carbon atoms or an aromatic group having 4 to 12 carbon atoms, respectively.)
In the general formulas (3) and (4), R ²⁰ to R ²² independently represent an aliphatic group having 1 to 12 carbon atoms or an aromatic group having 4 to 12 carbon atoms, respectively, but the aliphatic group and the aromatic group. A part of the hydrogen atom of the group may be substituted, and examples of the substituent include a halogen group such as an alkyl group, an acyl group and a fluorine group.

Specific examples of the sulfonic acid ester compound represented by the general formula (3) include 3-(5-(((phenylsulfonyl) oxy) imino) thiophen-2 (5H) -iriden) -2- (o). -Trill) Propanenitrile, 3-(5-(((Camfersulfonyl) oxy) imino) thiophen-2 (5H) -iriden) -2- (o-tolyl) Propanenitrile, 3-(5-(((Tori)) Fluoromethylsulfonyl) oxy) imino) thiophene-2 (5H) -iriden) -2- (o-tolyl) propanenitrile and the like can be mentioned, but are not limited thereto. Two or more of these may be contained.

Specific examples of the sulfonic acid ester compound represented by the general formula (4) include, but are not limited to, the following structures. Two or more of these may be contained.

Examples of the onium salt include a sulfonium salt and an iodonium salt. Specifically, for example, benzenesulfonic acid (4-hydroxyphenyl) dimethylsulfonium, benzenesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethylsulfonium, benzylsulfonic acid (4-hydroxyphenyl) methylsulfonium, benzene Benzyl Sulfonic Acid (4-((methoxycarbonyl) oxy) phenyl) methyl sulfonium, benzene sulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, camphor sulfonic acid (4-hydroxyphenyl) dimethyl sulfonium , Kamfer sulfonic acid (4-((methoxycarbonyl) oxy) phenyl) dimethyl sulfonium, benzyl benzene sulfonic acid (4-hydroxyphenyl) methyl sulfonium, benzyl camphor sulfonic acid (4-((methoxycarbonyl) oxy) phenyl) methyl sulfonium , Camper Sulfonic Acid (4-Hydroxyphenyl) Methyl ((2-Methylphenyl) Methyl) Sulfonium, Trifluoromethane Sulfonic Acid (4-Hydroxyphenyl) Dimethyl Sulfonium, Trifluoromethane Sulfonic Acid benzyl (4-Hydroxyphenyl) Methyl Sulfonium, Trifluo Benzyl lomethanesulfonic acid (4-((methoxycarbonyl) oxy) phenyl) methylsulfonium, trifluoromethanesulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, "San Aid"®, SI 145, SI-200, SI-250, SI-B2A, SI-B3A, SI-B3, SI-B4, SI-B5 (manufactured by Sanshin Chemical Industry Co., Ltd.), etc., but are not limited thereto. .. Two or more of these may be contained.

The content of the (B) thermal acid generator is from the viewpoint of further promoting the ring closure reaction of the benzooxazole precursor portion, and the resin composition of the present invention further contains the (C) thermal cross-linking agent described later. In the case of a resin composition, from the viewpoint of further promoting the cross-linking reaction with the (C) thermal cross-linking agent, 0.1 part by mass or more is preferable, and 0.3 part by mass or more is preferable with respect to 100 parts by mass of the component (A). Is more preferable, and 0.5 parts by mass or more is more preferable. On the other hand, from the viewpoint of maintaining the electrical insulation of the obtained cured film and suppressing peeling from the metal material in the cured film after the reliability test such as the high temperature storage test, with respect to 100 parts by mass of the component (A). 100 parts by mass or less is preferable, 8 parts by mass or less is more preferable, and 5 parts by mass or less is more preferable.

The resin composition of the present invention preferably further contains (C) a thermal cross-linking agent.

The (C) thermal cross-linking agent used in the present invention refers to a compound having at least two thermally reactive functional groups in the molecule, including an alkoxymethyl group, a methylol group, and an oxetanyl group. (C) The heat-crosslinking agent strongly crosslinks with the component (A) or other additive components including the component (D), and at the same time enhances the heat resistance, chemical resistance, hardness and compactness of the film after thermosetting. It is possible to suppress peeling from the metal material in the cured film after the reliability test such as the high temperature storage test.

When the resin composition of the present invention is a resin composition further containing (C) a heat-crosslinking agent, the above-mentioned (B) thermo-acid generator causes cross-linking between the component (A) and (C) the heat-crosslinking agent. It acts as a catalyst for accelerating the reaction, thereby improving the heat resistance, chemical resistance, and denseness of the cured film obtained by curing the resin composition of the present invention.

(C) As a thermal cross-linking agent, preferable examples of a compound having at least two alkoxymethyl groups or methylol groups include, for example, DML-PC, DML-PEP, DML-OC, DML-OEP, DML-34X, DML-. PTBP, DML-PCHP, DML-OCHP, DML-PFP, DML-PSBP, DML-POP, DML-MBOC, DML-MBPC, DML-MTrisPC, DML-BisOC-Z, DML-BisOCHP-Z, DML-BPC, DML-BisOC-P, DMOM-PC, DMOM-PTBP, DMOM-MBPC, TriML-P, TriML-35XL, TML-HQ, TML-BP, TML-pp-BPF, TML-BPE, TML-BPA, TML- BPAF, TML-BPAP, TMOM-BP, TMOM-BPE, TMOM-BPA, TMOM-BPAF, TMOM-BPAP, HML-TPPHBA, HML-TPHAP, HMOM-TPPHBA, HMOM-TPHAP (above, trade name, Honshu Chemical Industry) (Manufactured by Co., Ltd.), "NIKALAC" (registered trademark) MX-290, NIKALAC MX-280, NIKALAC MX-270, NIKALAC MX-279, NIKALAC MW-100LM, NIKALAC MX-750LM (hereinafter, trade name, Co., Ltd.) Sanwa Chemical) and the like.

(C) As a thermal cross-linking agent, preferable examples of a compound having at least two oxetanyl groups are "Denacol" (registered trademark) EX-212L, Denacol EX-214L, Denacol EX-216L, Denacol EX-850L, and Denacol EX. -321L (above, manufactured by Nagase ChemteX Corporation), GAN, GOT (above, manufactured by Nippon Kayaku Co., Ltd.), "Epicoat" (registered trademark) 828, Epicoat 1002, Epicoat 1750, Epicoat 1007, YX8100-BH30 , E1256, E4250, E4275 (all manufactured by Japan Epoxy Resin Co., Ltd.), "Epicron" (registered trademark) 850-S, Epicron HP-4032, Epicron HP-7200, Epicron HP-820, Epicron HP-4700, Epicron. HP-4770, Epicron HP4032 (above, manufactured by Dainippon Ink and Chemicals Co., Ltd.), VG3101 (manufactured by Mitsui Chemicals Co., Ltd.), "Tepic" (registered trademark) S, Tepic G, Tepic P (above, Nissan Chemical Industry Co., Ltd.) (Manufactured by Nippon Kayaku Co., Ltd.), NC6000 (manufactured by Nippon Kayaku Co., Ltd.), Epototo YH-434L (manufactured by Toto Kasei Co., Ltd.), EPPN502H, NC3000 (manufactured by Nippon Kayaku Co., Ltd.), Epicron N695, HP7200 (above, Examples include Dainippon Ink and Chemicals (manufactured by Dainippon Ink and Chemicals Co., Ltd.), "Etanacol" (registered trademark) EHO, Ethanacole OXBP, Ethanacole OXTP, Ethanacole OXMA (all manufactured by Ube Kosan Co., Ltd.), and oxetylated phenol novolac.

When the resin composition of the present invention is a resin composition further containing (C) a heat-crosslinking agent, the (C) heat-crosslinking agent has a structural unit represented by the following general formula (5). This is preferable because it is possible to further suppress peeling from the metal material in the cured film after a reliability test such as an improvement in elongation, low stress, and a high temperature storage test by densification of the obtained cured film. ..

(In the general formula (5), R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a methyl group. R ²³ is a divalent organic group having an alkylene group having 2 or more carbon atoms and is linear. , Branched, and cyclic. R ²³ is an alkylene group, a cycloalkylene group, an oxyalkylene group, an alkylsilylene group, an alkoxysilylene group, an arylene group, an oxyarylene group, an oxycarbonyl group, a carbonyl group, or an arylene group. , Vinylene group, a bonding group containing a heterocycle, a combination thereof, etc., and may further have a substituent.)
(C) Since the heat-crosslinking agent has a structural unit represented by the above general formula (5), the heat-crosslinking agent itself has a flexible alkylene group and a rigid aromatic group, so that it has heat resistance. It is possible to improve the elongation of the obtained cured film and reduce the stress. Examples of the cross-linking group include, but are not limited to, an acrylic group, a methylol group, an alkoxymethyl group, and an epoxy group. Among these, an epoxy group is preferable because it can react with the phenolic hydroxyl group of the component (A) to improve the heat resistance of the cured film and can react without dehydration.

Examples of the compound represented by the following general formula (5) include, but are not limited to, the following structures.

(In the formula, m is an integer of 1 to 5, and l is 1 to 20.)
Among the above structures, m is preferably 1 to 2 and l is preferably 3 to 7 from the viewpoint of achieving both heat resistance and improvement in elongation.

(C) Two or more kinds of thermal cross-linking agents may be used in combination.

The content of the (C) thermal cross-linking agent is preferably 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the component (A). (C) When the content of the thermal cross-linking agent is 1 part by mass or more and 100 parts by mass or less, the chemical resistance and hardness of the film after firing or curing can be increased, and the storage stability of the resin composition is improved. Can be made to.

The content of the compound represented by the general formula (5) is preferably 2 to 80 parts by mass, more preferably 5 to 60 parts by mass, based on 100 parts by mass of the total thermal crosslinking agent. By setting the content to 2 parts by mass or more, the effects of improving elongation and reducing stress can be obtained, and by setting the content to 80 parts by mass or less, it is possible to maintain the sensitivity of the resin composition. Become.

The resin composition of the present invention preferably further contains (D) a photosensitive compound. (D) Photosensitivity can be imparted to the resin composition by containing the photosensitive compound.

Examples of the (D) photosensitive compound include a compound having a group having a naphthoquinone diazide structure (hereinafter, may be referred to as a naphthoquinone diazide compound), a sulfonium salt, a phosphonium salt, a diazonium salt, an iodonium salt and the like. Further, a sensitizer or the like can be contained as needed.

As the naphthoquinone diazide compound, a naphthoquinone diazidosulfonyl ester compound in which the sulfonic acid of naphthoquinone diazidosulfonic acid is bonded to a compound having a phenolic hydroxyl group with an ester is preferable. Examples of the compound having a phenolic hydroxyl group used here include Bis-Z, BisP-EZ, TekP-4HBPA, TrisP-HAP, TrisP-PA, TrisP-SA, TrisOCR-PA, BisOCHP-Z, BisP-MZ, and BisP. -PZ, BisP-IPZ, BisOCP-IPZ, BisP-CP, BisRS-2P, BisRS-3P, BisP-OCHP, Methyltris-FR-CR, BisRS-26X, DML-MBPC, DML-MBOC, DML-OCHP, DML-PCHP, DML-PC, DML-PTBP, DML-34X, DML-EP, DML-POP, Dimethylol-BisOC-P, DML-PFP, DML-PSBP, DML-MTrisPC, TriML-P, TriML-35XL, TML-BP, TML-HQ, TML-pp-BPF, TML-BPA, TMOM-BP, HML-TPPHBA, HML-TPHAP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP-BIOC-F, 4PC, BIR-BIPC-F, TEP-BIP-A, 46DMOC, 46DMOEP, TM-BIP-A (trade name, Asahi Organic Materials Industry (trade name, Asahi Organic Materials Industry) Co., Ltd.), 2,6-dimethoxymethyl-4-tert-butylphenol, 2,6-dimethoxymethyl-p-cresol, 2,6-diacetoxymethyl-p-cresol, naphthol, tetrahydroxybenzophenone, methyl gallate Examples thereof include ester, bisphenol A, bisphenol E, methylene bisphenol, BisP-AP (trade name, manufactured by Honshu Chemical Industry Co., Ltd.). A naphthoquinone diazide sulfonyl ester compound obtained by introducing 4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazido sulfonic acid into these compounds having a phenolic hydroxyl group by an ester bond is exemplified as a preferable compound, but other compounds may be used. You can also.

Further, it is preferable that 50 mol% or more of the total phenolic hydroxyl group of the compound having a phenolic hydroxyl group is naphthoquinonediazidesulfonyl esterified. By using a naphthoquinone diazide compound in which 50 mol% or more of the phenolic hydroxyl groups of the compound having a phenolic hydroxyl group is sulfonyl esterified, the affinity of the naphthoquinone diazide compound with an alkaline aqueous solution is lowered, and the resin in the unexposed portion is used. The solubility of the composition in an alkaline aqueous solution is greatly reduced, and the naphthoquinone diazide structure portion of the naphthoquinone diazidesulfonyl group is changed to indencarboxylic acid by exposure to obtain a large dissolution rate of the resin composition in the exposed portion in the alkaline aqueous solution. As a result, the dissolution rate ratio between the exposed portion and the unexposed portion of the composition can be increased, and a pattern can be obtained with high resolution. By using such a naphthoquinone diazide compound, it is possible to obtain a resin composition having positive photosensitivity that is sensitive to i-line (365 nm), h-line (405 nm), and g-line (436 nm) of a general mercury lamp. can. Further, the photosensitive compound may be used alone or in combination of two or more, and a resin composition having high sensitivity can be obtained.

In the present invention, as the group having a naphthoquinone diazide structure, any of 5-naphthoquinone diazidosulfonyl group and 4-naphthoquinone diazidosulfonyl group is preferably used. The 5-naphthoquinone diazidosulfonyl ester compound has absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure and all-wavelength exposure. The 4-naphthoquinone diazidosulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazidosulfonyl ester compound or a 5-naphthoquinone diazidosulfonyl ester compound depending on the wavelength to be exposed. Further, a naphthoquinone diazidosulfonyl ester compound in which a 4-naphthoquinone diazidosulfonyl group and a 5-naphthoquinone diazidosulfonyl group are used in combination in the same molecule can also be used, or a 4-naphthoquinone diazidosulfonyl ester compound and a 5-naphthoquinone diazidosulfonyl ester compound can be used. Can also be used together.

The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a naphthoquinone diazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, the resolution, sensitivity, and residual film ratio are further improved.

The molecular weight of the compound (D) is preferably 300 or more, more preferably 350 or more, preferably 3,000 or less, and more preferably 1 from the viewpoint of heat resistance, mechanical properties, and adhesiveness of the film obtained by heat treatment. , 500 or less.

Of the photosensitive compounds, a sulfonium salt, a phosphonium salt, and a diazonium salt are preferable because they appropriately stabilize the acid component generated by exposure. Of these, the sulfonium salt is preferable.

The content of the compound (D) is preferably 0.1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the component (A). When the content of the compound (D) is 0.1 part by mass or more and 100 parts by mass or less, the photosensitivity can be imparted while maintaining the heat resistance, chemical resistance and mechanical properties of the film after the heat treatment.

When the compound (D) is a naphthoquinone diazide compound, the content of the naphthoquinone diazide compound is preferably 1 part by mass or more, more preferably 3 parts by mass or more, and preferably 100 parts by mass with respect to 100 parts by mass of the component (A). By mass or less, more preferably 80 parts by mass or less. When the amount is 1 part by mass or more and 80 parts by mass or less, the photosensitivity can be imparted while maintaining the heat resistance, chemical resistance and mechanical properties of the film after the heat treatment.

When the compound (D) is a sulfonium salt, a phosphonium salt, or a diazonium salt, the content of the sulfonium salt, the phosphonium salt, or the diazonium salt is preferably 0.1 part by mass or more with respect to 100 parts by mass of the component (A). It is preferably 1 part by mass or more, more preferably 3 parts by mass or more, preferably 100 parts by mass or less, more preferably 80 parts by mass or less, still more preferably 50 parts by mass or less. When the amount is 0.1 part by mass or more and 80 parts by mass or less, the photosensitivity can be imparted while maintaining the heat resistance, chemical resistance and mechanical properties of the film after the heat treatment.

The resin composition of the present invention may contain a compound having a phenolic hydroxyl group for the purpose of supplementing the alkali developability. Examples of the compound having a phenolic hydroxyl group include Bis-Z, BisOC-Z, BisOPP-Z, BisP-CP, Bis26X-Z, BisOTBP-Z, BisOCHP-Z, BisOCR-CP, BisP-MZ, and BisP-EZ. , Bis26X-CP, BisP-PZ, BisP-IPZ, BisCRIPZ, BisOCP-IPZ, BisOIPP-CP, Bis26X-IPZ, BisOTBP-CP, TekP-4HBPA (Tetrakiss P-DO-BPA), TrisPHAP, TrisP-PA, TrisP -PHBA, TrisP-SA, TrisOCR-PA, BisOFP-Z, BisRS-2P, BisPG-26X, BisRS-3P, BisOC-OCHP, BisPC-OCHP, Bis25X-OCHP, Bis26X-OCHP, BisOCHP-OC, Bis236T-OCP , Methylenetris-FR-CR, BisRS-26X, BisRS-OCHP, (trade name, manufactured by Honshu Kagaku Kogyo Co., Ltd.), BIR-OC, BIP-PC, BIR-PC, BIR-PTBP, BIR-PCHP, BIP. -BIOC-F, 4PC, BIRC-BIPC-F, TEP-BIP-A (trade name, manufactured by Asahi Organic Materials Industry Co., Ltd.), 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 2,4-dihydroxyquinoline, 2,6-dihydroxyquinoline, 2,3-dihydroxyquinoline Examples thereof include quinoxalin, anthracene-1,2,10-triol, anthracene-1,8,9-triol, 8-quinolinol and the like.

The resin composition containing the compound (D) used in the present invention contains these compounds having a phenolic hydroxyl group, so that it is hardly dissolved in an alkaline developer before exposure and is easily dissolved in an alkaline developer when exposed. Since it dissolves in, there is little film loss due to development, and development becomes easy in a short time. Therefore, the sensitivity is likely to be improved.

The resin composition of the present invention further contains (E) an antioxidant. (E) By containing an antioxidant, the oxidative deterioration of the aliphatic group and the phenolic hydroxyl group of the component (A) is suppressed. Further, due to the rust preventive action on the metal material, it is possible to suppress metal oxidation due to moisture from the outside, a photosensitizer, a thermal acid generator, etc., and the accompanying deterioration of adhesion and peeling. As the (E) antioxidant, the compound represented by the general formula (6) is preferable. By containing the compound represented by the general formula (6), it is possible to suppress the mechanical properties and peeling from the metal material in the cured film after the reliability test such as the high temperature storage test.

(In the general formula (6), R ²⁶ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, R ²⁷ represents an alkylene group having 2 or more carbon atoms, and R ²⁸ represents an alkylene group having 2 or more carbon atoms, O. Indicates a 1- to 4-valent organic group containing at least one of an atom and an N atom. K indicates an integer of 1 to 4. Suitable monovalent organic groups for R ²⁸ include an alkyl group and a cycloalkyl. A group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl group, an aryl ether group, a carboxyl group, an allyl group, a vinyl group, a heterocyclic group, etc. -O-, -NH-, -NHNH-, ^-NHCO- , -COO- and the like can be mentioned. Examples of the trivalent or tetravalent organic group suitable for R28 include the above-mentioned monovalent or divalent organic group. Examples thereof include a group in which hydrogen in the above is replaced with a bond point. Further, a group in which these groups are combined may be mentioned, and further, a substituent may be provided. Among them, solubility in a developing solution and adhesion to a metal are mentioned. From the viewpoint of properties, it is preferable to have an alkyl ether, -NH-, and from the viewpoint of interaction with the component (A) and metal adhesion due to metal complex formation, -NH- is more preferable.)
Examples of the compound represented by the general formula (6) include, but are not limited to, the following.

The content of the (E) antioxidant is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 5 parts by mass with respect to 100 parts by mass of the component (A). When the content is 0.1 part by mass or more, the adhesion to the metal material is improved and peeling is suppressed. Further, when the content is 10 parts by mass or less, the sensitivity of the resin composition can be maintained.

The resin composition of the present invention may contain a post-development adhesion improver, if necessary.

Post-development adhesion improvers include vinyltrimethoxysilane, vinyltriethoxysilane, epoxycyclohexylethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and p-styryltrimethoxy. Silane coupling agents such as silane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, titanium chelating agents, aluminum chelating agents, aromatic amine compounds and alkoxy. Examples thereof include a compound obtained by reacting a group-containing silicon compound. Two or more of these may be contained. By containing these post-development adhesion improvers, it is possible to improve the adhesion to a base material such as a silicon wafer, ITO, SiO ₂ , or silicon nitride when developing a resin film. In addition, it is possible to increase the resistance to oxygen plasma and UV ozone treatment used for cleaning and the like.

The content of the adhesion improver after development is preferably 0.01 to 50 parts by mass with respect to 100 parts by mass of the component (A). Within such a range, the effects of the respective post-development adhesion improvers can be fully exhibited.

Further, the resin composition of the present invention may contain an adhesion improver after curing.

The post-curing adhesion improver preferably contains a compound represented by the following general formula (7).

(In the general formula (7), R ²⁹ to R ³¹ represent either an O atom, an S atom, or an N atom, and at least one of R ²⁹ to R ³¹ represents an S atom. T represents 0 or 1. , U and v represent integers of 1 or 2. R ³² to R ³⁴ each independently represent a hydrogen atom or an organic group having 1 to 20 carbon atoms. R ³² to R ³⁴ are hydrogen atoms. , Alkyl group, cycloalkyl group, alkoxy group, alkyl polyether group, alkylsilyl group, alkoxysilyl group, aryl group, aryl ether group, carboxyl group, carbonyl group, allyl group, vinyl group, heterocyclic group, and their combination. It may also have a substituent.)
By containing the compound represented by the general formula (7), the adhesion between the film after heat curing and the metal material, particularly copper, can be remarkably improved and peeling can be suppressed. This is derived from the fact that the S and N atoms of the compound represented by the general formula (7) efficiently interact with the metal surface, and the three-dimensional structure is more likely to interact with the metal surface. caused by. Due to these effects, the resin composition of the present invention can obtain a cured film having excellent adhesiveness to a metal material.

Examples of the compound represented by the general formula (7) include the following, but the compound is not limited to the following structure.

The resin composition of the present invention may contain other post-curing adhesion improver in addition to the compound represented by the general formula (7). Examples of other post-curing adhesion improvers include an alkoxysilane-containing aromatic amine compound, an aromatic amide compound, and an aromatic-free silane compound. Two or more of these may be contained. By containing these compounds, the adhesiveness to the substrate after firing or curing can be improved.

Specific examples of the alkoxysilane-containing aromatic amine compound and the aromatic amide compound are shown below. In addition to this, it may be a compound obtained by reacting an aromatic amine compound with an alkoxy group-containing silicon compound. For example, an aromatic amine compound and a group that reacts with an amino group such as an epoxy group or a chloromethyl group may be used. Examples thereof include a compound obtained by reacting the possessing alkoxysilane compound.

Examples of the aromatic-free silane compound include vinyl silane compounds such as vinyl trimethoxysilane, vinyl triethoxysilane, vinyl trichlorosilane, and vinyltris (β-methoxyethoxy) silane, 3-methacryloxypropyltrimethoxysilane, and 3-acryloxypropyl. Examples thereof include carbon-carbon unsaturated bond-containing silane compounds such as trimethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. Among these, vinyltrimethoxysilane and vinyltriethoxysilane are preferable.

The content of the post-curing adhesive improver represented by the general formula (7) used in the resin composition of the present invention is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the component (A). It is preferable that the content of the adhesion improver after curing is 0.1 part by mass or more with respect to 100 parts by mass of the component (A), because the effect of adhesion to a metal material or the like can be sufficiently obtained. Further, by setting the content of the adhesion improver after curing to 10 parts by mass or less with respect to 100 parts by mass of the component (A), when the resin composition used in the present invention is a positive photosensitive resin composition. , The decrease in sensitivity of the resin composition before curing can be suppressed by the interaction with the photosensitive agent.

Here, the content of the other post-curing adhesive improver is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the component (A). Within such a range, the adhesiveness with the substrate after firing or curing can be improved. It can also contain compounds such as vinyltrimethoxysilane and vinyltriethoxysilane that act as post-development adhesion improvers and post-curing adhesion improvers.

The resin composition of the present invention may contain a surfactant, if necessary, for the purpose of improving the wettability with the substrate and improving the film thickness uniformity of the coating film. Commercially available compounds can be used as the surfactant. Specifically, the silicone-based surfactants include SH series, SD series, ST series of Toray Dow Corning Silicone, BYK series of Big Chemie Japan, and Shinetsu Silicone. KP series of Nippon Oil & Fats, Disform series of Nippon Oil & Fats, TSF series of Toshiba Silicone, etc. As fluorine-based surfactants, "Megafuck" (registered trademark) series of Dainippon Ink Industry Co., Ltd., Sumitomo 3M Florard series, Asahi Glass's "Surfron" (registered trademark) series, "Asahiguard" (registered trademark) series, Shin-Akita Kasei's EF series, Omniova Solution's Polyfox series, etc. Examples of the surfactant obtained from the system and / or the methacryl-based polymer include, but are not limited to, the Polyflow series of Kyoeisha Chemical Co., Ltd. and the "Disparon" (registered trademark) series of Kusumoto Kasei Co., Ltd.

The content of the surfactant is preferably 0.001 part by mass or more and 1 part by mass or less with respect to 100 parts by mass of the component (A). Within the above range, the wettability with the substrate and the uniformity of the film thickness of the coating film can be improved without causing problems such as air bubbles and pinholes.

The resin composition of the present invention may contain other alkali-soluble resin in addition to the component (A). Specifically, an alkali-soluble polyimide, polybenzoxazole, an acrylic polymer copolymerized with acrylic acid, a novolak resin, a resole resin, a polymer containing a radically polymerizable monomer having an alkali-soluble group, a siloxane resin, and a cyclic olefin resin. Examples thereof include a resin having a cardo structure, that is, a skeleton structure in which two cyclic structures are bonded to a quaternary carbon atom constituting the cyclic structure. Such resins are soluble in alkaline solutions such as tetramethylammonium hydroxide, choline, triethylamine, dimethylaminopyridine, monoethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate and the like. By containing these alkali-soluble resins, the characteristics of each alkali-soluble resin can be imparted while maintaining the adhesion and excellent sensitivity of the cured film.

The resin composition of the present invention preferably contains a solvent. As the solvent, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2. -Polar aprotonic solvents such as imidazolidinone, N, N'-dimethylpropylene urea, N, N-dimethylisobutyric acid amide, methoxy-N, N-dimethylpropionamide, tetrahydrofuran, dioxane, propylene glycol monomethyl ether, propylene Ethers such as glycol monoethyl ether, ketones such as acetone, methyl ethyl ketone and diisobutyl ketone, esters such as ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, propylene glycol monomethyl ether acetate and 3-methyl-3-methoxybutyl acetate. Examples include alcohols such as ethyl lactate, methyl lactate, diacetone alcohol, 3-methyl-3-methoxybutanol, aromatic hydrocarbons such as toluene and xylene, and the like. Two or more of these may be contained.

The content of the solvent is preferably 100 parts by mass or more in order to dissolve the composition in 100 parts by mass of the component (A), and 1,500 parts by mass in order to form a coating film having a film thickness of 1 μm or more. It is preferable to contain a portion or less.

Next, a method for producing the resin composition of the present invention will be described. For example, each component (A), (B) and (E), preferably each component (C) to (D), and if necessary, a compound having a phenolic hydroxyl group, a post-development adhesion improver, and curing. A resin composition can be obtained by dissolving a post-adhesive improver, a surfactant, other resins, a solvent and the like. Examples of the melting method include heating and stirring. When heating, the heating temperature is preferably set within a range that does not impair the performance of the photosensitive colored resin composition, and is usually room temperature to 80 ° C. Further, the dissolution order of each component is not particularly limited, and for example, there is a method of sequentially dissolving compounds having low solubility. When stirring, the rotation speed is preferably set within a range that does not impair the performance of the photosensitive colored resin composition, and is usually 200 rpm to 2000 rpm. It may be agitated or heated as needed, and is usually at room temperature to 80 ° C. In addition, for components that tend to generate bubbles during stirring and dissolution, such as surfactants and some post-development adhesion improvers, by dissolving other components and then adding them last, other components due to the generation of bubbles can be removed. It is possible to prevent poor dissolution.

The viscosity of the resin composition of the present invention is preferably 2 to 5,000 mPa · s. By adjusting the solid content concentration so that the viscosity is 2 mPa · s or more, it becomes easy to obtain a desired film thickness. On the other hand, when the viscosity is 5,000 mPa · s or less, it becomes easy to obtain a highly uniform coating film. A resin composition having such a viscosity can be easily obtained, for example, by setting the solid content concentration to 5 to 60% by mass.

The obtained resin composition is preferably filtered using a filtration filter to remove dust and particles. The filter hole diameter is, for example, 0.5 μm, 0.2 μm, 0.1 μm, 0.05 μm, 0.02 μm, and the like, but is not limited thereto. The material of the filtration filter includes polypropylene (PP), polyethylene (PE), nylon (NY), polytetrafluoroethylene (PTFE) and the like, but polyethylene and nylon are preferable.

Next, a method for producing a cured film using the resin composition of the present invention, a resin film formed from the resin composition, or a resin sheet will be described.

Here, the resin film is defined as a film obtained by applying the resin composition of the present invention on a substrate and drying it. A resin sheet is defined as a sheet obtained by applying a resin composition on a peelable base material and drying it. Further, the cured film is defined as a resin film or a film obtained by curing a resin sheet.

The resin composition of the present invention is applied to a substrate to obtain a coating film of the resin composition. As the substrate, silicon wafers, ceramics, gallium arsenide, organic circuit boards, inorganic circuit boards, and those on which circuit constituent materials are arranged are used, but the substrate is not limited thereto. As a coating method, there are a spin coating method, a slit coating method, a dip coating method, a spray coating method, a printing method and the like. The coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 0.1 to 150 μm.

Prior to coating, the substrate to which the resin composition is applied may be pretreated with the above-mentioned post-development adhesion improver. For example, a solution in which a post-development adhesion improver is dissolved in a solvent such as isopropanol, ethanol, methanol, water, tetrahydrofuran, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diethyl adipate in an amount of 0.5 to 20% by mass. Examples thereof include a method of treating the surface of the substrate by a method such as spin coating, slit die coating, bar coating, dip coating, spray coating, and steam treatment. If necessary, a vacuum drying treatment is performed, and then a heat treatment at 50 ° C. to 280 ° C. is performed to allow the reaction between the substrate and the post-development adhesion improver to proceed.

Next, the coating film of the resin composition is dried to obtain a resin film. Drying is preferably carried out in the range of 50 ° C. to 140 ° C. for 1 minute to several hours using an oven, a hot plate, infrared rays or the like.

On the other hand, when a resin sheet formed from the resin composition of the present invention is used, if the resin sheet has a protective film, it is peeled off, the resin sheet and the substrate face each other, and they are bonded by thermocompression bonding (with the resin sheet). Laminating the resin sheet on the base material may be described as laminating the resin sheets on the base material with the substrates facing each other and being bonded by thermocompression bonding). Next, the resin sheet laminated on the base material is dried in the same manner as in obtaining the resin film to form the resin film. The resin sheet can be obtained by applying the resin composition of the present invention on a support film made of polyethylene terephthalate or the like as a peelable base material and drying it.

Thermocompression bonding can be performed by a hot press treatment, a hot laminating treatment, a hot vacuum laminating treatment, or the like. The bonding temperature is preferably 40 ° C. or higher from the viewpoint of adhesion to the substrate and embedding property. Further, when the resin sheet has photosensitive property, the bonding temperature is preferably 140 ° C. or lower in order to prevent the resin sheet from being cured at the time of bonding and the resolution of pattern formation in the exposure / developing process from being lowered.

When the resin film is photosensitive, the chemical beam is irradiated through a mask having a desired pattern on the film. Chemical rays used for exposure include ultraviolet rays, visible rays, electron beams, X-rays, etc., but in the present invention, g-rays (436 nm), h-rays (405 nm), and i-rays (365 nm), which are common exposure wavelengths, are used. , Is preferably used.

Next, the exposed photosensitive resin film is developed and the exposed portion is removed. The developing solution is tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate. , An aqueous solution of an alkaline compound such as cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable. In some cases, these alkaline aqueous solutions may be mixed with polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolactone and dimethylacrylamide, methanol, ethanol, etc. It may contain one or more alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, and ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone. After development, it is common to rinse with water. Here, too, alcohols such as ethanol and isopropyl alcohol, and esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water for rinsing.

The resin film thus obtained is subjected to a thermal cross-linking reaction by applying a temperature of 140 ° C. to 280 ° C. to improve heat resistance and chemical resistance (this step may be referred to as a heat treatment step). This heat treatment is carried out for 5 minutes to 5 hours while selecting a temperature and gradually raising the temperature, or selecting a certain temperature range and continuously raising the temperature. As an example, heat treatment is performed at 130 ° C. and 200 ° C. for 30 minutes each. The cure conditions in the present invention are preferably 140 ° C. or higher and 280 ° C. or lower. The cure conditions are preferably 140 ° C. or higher, more preferably 160 ° C. or higher, in order to promote the thermal crosslinking reaction. Further, the present invention is particularly preferably at 280 ° C. or lower, preferably 250 ° C., in order to provide an excellent cured film by curing at a low temperature, suppress malfunctions due to thermal history of the semiconductor device described later, and improve the yield. The following is more preferable, and 220 ° C. or lower is further preferable.

The cured film obtained by curing the resin composition or the resin sheet of the present invention can be used for electronic components such as semiconductor devices and multilayer wiring boards. Specifically, it is suitable for applications such as a semiconductor passive film (interlayer insulating film, surface protective film), a semiconductor element protective film (sometimes referred to as a semiconductor protective film), and an interlayer insulating film for high-density mounting multilayer wiring. Used for. Examples of the electronic device having the surface protective film and the interlayer insulating film on which the cured film of the present invention is arranged include MRAM having low heat resistance. That is, the cured film of the present invention is suitable for the surface protective film of MRAM. In addition to MRAM, polymer memory (PFRAM) and phase change memory (PCRAM, or Ovonics Unified Memory: OUM), which are promising next-generation memories, are also heat-resistant compared to conventional memory. It is likely to use low new materials. Therefore, the cured film of the present invention is also suitable for these surface protective films. Further, a display device including a first electrode formed on the substrate and a second electrode provided facing the first electrode, specifically, for example, an LCD, an ECD, an ELD, or an organic electroluminescent element. It can be used for an insulating layer such as the display device (organic electroluminescent device) used. In particular, in recent years, semiconductor devices having copper electrodes, copper wiring, and bumps have become the mainstream in semiconductor element electrodes, multilayer wiring, and circuit board wiring due to further miniaturization of the structure, and etching of copper and barrier metal. When forming the pattern of the resist, it is in a state of being in contact with many chemicals such as flux. When the resin film formed by the resin composition of the present invention is used as a protective film for such electrodes and wiring, it is particularly preferably used because it has high resistance to those chemicals.

Next, the resin composition of the present invention or the cured film obtained by curing the resin sheet will be described with reference to an application example to a semiconductor device having bumps. FIG. 1 is an enlarged cross-sectional view of a pad portion of a semiconductor device having bumps. As shown in FIG. 1, in the silicon wafer 1, a passivation film 3 is formed on an aluminum pad (hereinafter, Al pad) 2 for input / output, and a via hole is formed in the passivation film 3. Further, an insulating film 4 formed by using the resin composition or the resin sheet of the present invention is formed on the insulating film 4, and the metal film 5 formed of Cr, Ti, or the like is connected to the Al pad 2. It is formed. Each pad is insulated by etching the periphery of the solder bump 10 of the metal film 5. A barrier metal 8 and a solder bump 10 are formed on the insulated pad. When the flexible component is introduced into the resin composition, the warp of the wafer is small, so that exposure and transportation of the wafer can be performed with high accuracy. In addition, since polyimide resin and polybenzoxazole resin have excellent mechanical properties, stress from the sealing resin can be relieved even during mounting, so they are used as a low-k layer (interlayer insulating film material inside semiconductor devices). A layer made of a material having a low dielectric constant) can be prevented from being damaged, and a highly reliable semiconductor device can be provided.

Next, a detailed manufacturing method of the semiconductor device will be described. In the step 2a of FIG. 2, the resin composition of the present invention is applied onto the silicon wafer 1 on which the Al pad 2 and the passivation film 3 are formed, and the patterned insulating film 4 is formed through the photolithography step. Then, in the step 2b, the metal film 5 is formed by a sputtering method. As shown in 2c of FIG. 2, a metal wiring 6 is formed on the metal film 5 by a plating method. Next, as shown in 2d'of FIG. 2, the resin composition of the present invention is applied or a resin sheet is attached, and the insulating film 7 is formed as a pattern as shown in 2d of FIG. 2 through a photolithography step. At this time, the resin composition of the insulating film 7 is subjected to thick film processing on the scribe line 9. Wiring (so-called rewiring) can be further formed on the insulating film 7. When forming a multi-layer wiring structure having two or more layers, the rewiring of two or more layers is separated by the interlayer insulating film obtained from the resin composition or the resin sheet of the present invention by repeating the above steps. It is also possible to form a semiconductor electronic component or a semiconductor device having a multi-layer wiring structure (that is, rewiring and two or more layers of interlayer insulating films are repeatedly arranged). At this time, the formed insulating film comes into contact with various chemicals a plurality of times, but the insulating film obtained from the resin composition of the present invention has excellent adhesion and chemical resistance, and is therefore good. A multi-layer wiring structure can be formed. There is no upper limit to the number of layers in the multi-layer wiring structure, but those with 10 or less layers are often used.

Next, as shown in 2e and 2f of FIG. 2, the barrier metal 8 and the solder bump 10 are formed. Then, dicing along the scribe line 9 is performed to cut each chip. If the insulating film 7 does not have a pattern formed on the scribe line 9 or a residue remains, cracks or the like occur during dicing, which affects the reliability of the chip. Therefore, it is very preferable to be able to provide excellent pattern processing for thick film processing as in the present invention in order to obtain high reliability of the semiconductor device.

The resin composition of the present invention is also suitably used for a fan-out wafer level package (fan-out WLP).

FIG. 3 is a cross-sectional view of a manufacturing process of a semiconductor device showing an embodiment of the present invention. More specifically, it is an enlarged cross-sectional view of a pad portion of a semiconductor device having an insulating film of the present invention, and has a structure called a fan-out wafer level package (fan-out WLP). Similar to the above application example 1, the silicon wafer 1 on which the Al pad 2 and the passivation film 3 are formed is diced, cut into pieces for each chip, and then sealed with the resin 11. An insulating film 4 is formed on the sealing resin 11 and the chip as a pattern by the photosensitive resin composition of the present invention, and further, a metal (Cr, Ti, etc.) film 5 and a metal wiring 6 are formed. .. After that, the barrier metal 8 and the solder bump 10 are formed in the opening of the insulating film 7 formed on the sealing resin outside the chip.

In the fan-out WLP, an expansion portion is provided around the semiconductor chip using a sealing resin such as epoxy resin, rewiring is performed from the electrode on the semiconductor chip to the expansion portion, and a solder ball is also mounted on the expansion portion. It is a semiconductor package that secures the required number of terminals. In the fan-out WLP, wiring is installed so as to straddle the boundary line formed by the main surface of the semiconductor chip and the main surface of the sealing resin. That is, an interlayer insulating film is formed on an adjacent base material (substrate) composed of two or more kinds of materials such as a semiconductor chip to which metal wiring is applied and a sealing resin, and wiring is formed on the interlayer insulating film. It is formed. In addition to this, in a type of semiconductor package in which a semiconductor chip is embedded in a recess formed in a glass epoxy resin substrate, wiring is installed so as to straddle the boundary line between the main surface of the semiconductor chip and the main surface of the printed circuit board. .. Also in this embodiment, an interlayer insulating film is formed on an adjacent base material (substrate) composed of two or more kinds of materials, and wiring is formed on the interlayer insulating film. In this way, in semiconductor electronic components or semiconductor devices, the cured film obtained by curing the resin composition of the present invention has high adhesion to semiconductor chips to which metal wiring is applied, and can be used as a sealing resin for epoxy resin or the like. Since it also has a high adhesion, it is suitably used as an interlayer insulating film provided on an adjacent base material (substrate) composed of two or more kinds of materials.

Further, the resin composition of the present invention is also suitably used for coil parts of an inductor device.

FIG. 4 is a cross-sectional view of a coil component of an inductor device showing an embodiment of the present invention.
As shown in FIG. 4, an insulating film 13 is formed on the substrate 12, and an insulating film 14 is formed as a pattern on the insulating film 13. Ferrite or the like is used as the substrate 12. The photosensitive resin composition of the present invention may be used for either the insulating film 13 or the insulating film 14. A metal (Cr, Ti, etc.) film 15 is formed at the opening of this pattern, and a metal wiring (Ag, Cu, etc.) 16 is plated and formed on the metal (Cr, Ti, etc.) film 15. The metal wiring 16 (Ag, Cu, etc.) is formed on a spiral. By repeating the steps of forming 13 to 16 a plurality of times and laminating them, the function as a coil can be obtained. Finally, the metal wiring 16 (Ag, Cu, etc.) is connected to the electrode 18 by the metal wiring 17 (Ag, Cu, etc.) and is sealed by the sealing resin 19.

Hereinafter, the present invention will be described with reference to examples and the like, but the present invention is not limited to these examples. The resin composition in the examples was evaluated by the following method. For the evaluation, a resin composition (hereinafter referred to as varnish) filtered with a 1 μm polytetrafluoroethylene filter (manufactured by Sumitomo Electric Industries, Ltd.) was used.

(1) Calculation of ring closure rate of cured film Apply varnish on an 8-inch silicon wafer by spin coating using a coating developer ACT-8 so that the film thickness after prebaking at 120 ° C for 3 minutes is 11 μm. After coating and prebaking, the temperature is raised to 200 ° C. or 220 ° C. at 4.0 ° C./min at an oxygen concentration of 20 ppm or less using an inertia oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.) to 200 ° C. Alternatively, heat treatment was performed at 220 ° C. for 1 hour. When the temperature became 50 ° C. or lower, the silicon wafer was taken out to obtain a cured film (A). Further, a cured film (B) heated at 300 to 350 ° C. was obtained. The infrared absorption spectra of these cured films (A) and the cured film (B) were measured, and the absorbance of the peak caused by the CO expansion and contraction vibration near 1050 cm ^-1 was determined. For the measurement of the infrared absorption spectrum, "FT-720" (trade name, manufactured by HORIBA, Ltd.) was used as a measuring device. The ring closure rate of the cured film (A) was calculated from the following formula, assuming that the ring closure rate of the cured film (B) was 100%. The ring closure rate referred to here is the ring closure rate of a poly (o-hydroxyamide) structural unit.

In this example, a cured film was prepared from varnish as described above, and the ring closure rate was calculated.

Those having a ring closure rate of 40% or more were evaluated as extremely good, those having a ring closure rate of 30% or more and less than 40% were evaluated as good, and those having a ring closure rate of less than 30% were evaluated as poor.

The heating temperature for obtaining the cured film (B) is preferably 320 ° C. if the cured film is not thermally decomposed. The thermal decomposition temperature of the cured film can be analyzed by thermogravimetric analysis (TGA).

(2) Evaluation of heat resistance Apply varnish on an 8-inch silicon wafer by spin-coating and pre-baking using a developing device ACT-8 so that the film thickness after pre-baking at 120 ° C for 3 minutes is 11 μm. Then, using an inert oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), the temperature was raised to 200 ° C. or 220 ° C. at 4.0 ° C./min at an oxygen concentration of 20 ppm or less, and then 200 ° C. or 220 ° C. Was heat-treated for 1 hour. When the temperature became 50 ° C. or lower, the silicon wafer was taken out and immersed in 45% by mass of hydrofluoric acid for 5 minutes to peel off the cured film of the resin composition from the wafer. This film is cut into strips with a width of 0.5 cm and a length of 10 cm, and heated from room temperature to 400 ° C. at a heating rate of 10 ° C./min using a thermogravimetric measuring device TGDTA6200 (manufactured by Hitachi High-Tech Science Co., Ltd.). The 5% weight loss temperature was measured.

A value of 5% weight loss temperature of 315 ° C. or higher was evaluated as good, and a value of less than 315 ° C. was evaluated as poor.

(3) Evaluation of chemical resistance The varnish was applied on a silicon wafer by a spin coating method using a coating developer ACT-8 so that the film thickness after prebaking at 120 ° C. for 3 minutes was 10 μm. After prebaking, the temperature is raised to 200 ° C. or 220 ° C. at 4.0 ° C./min at an oxygen concentration of 20 ppm or less under a nitrogen stream using an inert oven CLH-21CD-S, and heated at 200 ° C. or 220 ° C. for 1 hour. Processing was performed. When the temperature drops below 50 ° C, the silicon wafer is taken out and the cured film is immersed in an organic chemical solution (dimethyl sulfoxide: 25% tetramethylammonium hydroxide aqueous solution = 92: 2) at 65 ° C for 100 minutes to peel off the pattern. The presence or absence of elution was observed.

The result was evaluated as good when there was no pattern peeling or elution, and as poor when pattern peeling or elution was observed.

(4) -1. Breaking point elongation evaluation After applying and prebaking the varnish on an 8-inch silicon wafer by the spin coating method using a coating developer ACT-8 so that the film thickness after prebaking at 120 ° C. for 3 minutes is 11 μm. Using the Inert Oven CLH-21CD-S (manufactured by Koyo Thermo System Co., Ltd.), the temperature is raised to 200 ° C. or 220 ° C. at 4.0 ° C./min at an oxygen concentration of 20 ppm or less, and 1 at 200 ° C. or 220 ° C. The time heat treatment was performed. When the temperature became 50 ° C. or lower, the silicon wafer was taken out and immersed in 45% by mass of hydrofluoric acid for 5 minutes to peel off the cured film of the resin composition from the wafer. This film is cut into strips having a width of 1 cm and a length of 9 cm, and using Tencilon RTM-100 (manufactured by Orientec Co., Ltd.), the tensile speed is 50 mm / at a room temperature of 23.0 ° C. and a humidity of 45.0% RH. It was pulled in minutes and the break point elongation was measured. The measurement was performed on 10 strips per sample, and the average value of the top 5 points was obtained from the results.

Those having a breaking point elongation value of 60% or more were evaluated as extremely good, those having a breaking point elongation value of 40% or more and less than 60% were evaluated as good, and those having a breaking point elongation value of less than 40% were evaluated as poor.

(4) -2. Evaluation of peeling in copper wiring after high temperature storage test (High Temperature Storage, HTS) The following evaluation boards were prepared for evaluation of peeling in copper wiring.

Cylindrical copper wirings having a thickness of 5 μm and a diameter of 90 μm were made on an 8-inch silicon wafer at equal intervals so that the distance between the centers of the copper wirings was 150 μm. This was used as an evaluation substrate.

The varnish is applied and prebaked on the above evaluation substrate by a spin coating method using a coating developer ACT-8 so that the film thickness after prebaking at 120 ° C. for 3 minutes is 11 μm, and then the inert oven CLH-21CD-. Using S (manufactured by Koyo Thermo System Co., Ltd.), the temperature was raised at 200 ° C. at 4.0 ° C./min at an oxygen concentration of 20 ppm or less, and heat treatment was performed at 200 ° C. for 1 hour. When the temperature became 50 ° C. or lower, the evaluation substrate (hereinafter referred to as a sample) was taken out. Next, the sample was put into a constant temperature bath at 175 ° C. and treated for 200 hours. After that, in order to take out the sample and observe the peeling in the copper wiring, the scanning electron microscope FEI Helios650 (manufactured by FEI Co., Ltd.) attached to the focused ion beam processing device was used to cut the sample and increase the magnification to 40,000 times. The cross section was observed. As an evaluation method, the degree of peeling of the side surface of the copper wiring is observed, and the peeling of 0% or more and less than 25% is regarded as extremely good 3, the peeling of 25% or more and less than 50% is regarded as good 2, and the peeling of 50% is regarded as good. It was evaluated as 1 as a defect.

<Synthesis Example 1 Synthesis of Hydroxyl Group-Containing Diamine Compound>
2,2-Bis (3-amino-4-hydroxyphenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., hereinafter referred to as BAHF) 18.3 g (0.05 mol), 100 mL of acetone, propylene oxide (Tokyo) It was dissolved in 17.4 g (0.3 mol) (manufactured by Kasei Co., Ltd.) and cooled to −15 ° C. A solution prepared by dissolving 20.4 g (0.11 mol) of 3-nitrobenzoyl chloride (manufactured by Tokyo Kasei Co., Ltd.) in 100 mL of acetone was added dropwise thereto. After completion of the dropping, the mixture was stirred at −15 ° C. for 4 hours and then returned to room temperature. The precipitated white solid was filtered off and vacuum dried at 50 ° C.

30 g of the obtained white solid was placed in a 300 mL stainless autoclave, dispersed in 250 mL of methyl cell solve, and 2 g of 5% palladium-carbon (manufactured by Wako Pure Chemical Industries, Ltd.) was added. Hydrogen was introduced here with a balloon and the reduction reaction was carried out at room temperature. After about 2 hours, the reaction was terminated after confirming that the balloon did not deflate any more. After completion of the reaction, the palladium compound as a catalyst was removed by filtration and concentrated with a rotary evaporator to obtain a hydroxyl group-containing diamine compound represented by the following formula.

<Synthesis Example 2 Synthesis of Polyimide Precursor (A-1)>
Under a dry nitrogen stream, 31.0 g (0.10 mol) of 3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride (hereinafter referred to as ODPA) was dissolved in 500 g of NMP. Here, 39.30 g (0.065 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to 50 g of NMP. In addition, the reaction was carried out at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. Subsequently, RT-1000 (10.00 g, 0.010 mol) containing a propylene oxide and a tetramethylene ether glycol structure was added together with 10 g of NMP, and the mixture was reacted at 50 ° C. for 1 hour. Next, 4.36 g (0.04 mol) of 4-aminophenol as an end-capping agent was added together with 5 g of NMP, and the mixture was reacted at 50 ° C. for 2 hours. Then, a solution of 28.6 g (0.24 mol) of N, N-dimethylformamide dimethylacetal diluted with 50 g of NMP was added dropwise over 10 minutes. After the dropping, the mixture was stirred at 50 ° C. for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 24 hours to obtain a polyimide precursor (A-1) which is a target alkali-soluble resin.

<Synthesis Example 3 Synthesis of Polybenzoxazole Precursor (A-2)>
Under a dry nitrogen stream, 27.47 g of BAHF (0.075 mol) was dissolved in 257 g of NMP. To this, 1,1'-(4,4'-oxybenzoyl) imidazole (hereinafter referred to as PBOM) (17.20 g, 0.048 mol) was added together with 20 g of NMP, and the mixture was reacted at 85 ° C. for 3 hours. Subsequently, RT-1000 (20.00 g, 0.020 mol) containing propylene oxide and tetramethylene ether glycol structure, 1,3-bis (3-aminopropyl) tetramethyldisiloxane (1.24 g, 0.005). Mole), PBOM (14.33 g, 0.044 mol) was added with 50 g of NMP and reacted at 85 ° C. for 1 hour. Further, as a terminal sealant, 5-norbornene-2,3-dicarboxylic acid anhydride (3.94 g, 0.024 mol) was added together with 10 g of NMP and reacted at 85 ° C. for 30 minutes. After completion of the reaction, the mixture was cooled to room temperature, acetic acid (52.82 g, 0.50 mol) was added together with 87 g of NMP, and the mixture was stirred at room temperature for 1 hour. After the stirring was completed, the solution was poured into 3 L of water to obtain a white precipitate. The precipitate was collected by filtration, washed with water three times, and then dried in a ventilation dryer at 50 ° C. for 3 days to obtain a powder of the polybenzoxazole precursor (A-2).

<Synthesis Example 4 Synthesis of Polybenzoxazole Precursor (A-3)>
According to Synthetic Example 3, ED-900 (9.00 g, 0.020 mol) containing BAHF (27.47 g, 0.075 mol), PBOM (30.10 g, 0.084 mol), propylene oxide and ethylene glycol structure. ), 1,3-Bis (3-aminopropyl) tetramethyldisiloxane (1.24 g, 0.0050 mol), 5-norbornen-2,3-dicarboxylic acid anhydride (5.25 g, 0.032 mol) , Acetic acid (48.02 g, 0.80 mol) and NMP409 g were used in the same manner to obtain a powder of the polybenzoxazole precursor (A-3).

<Synthesis Example 5 Synthesis of Polybenzoxazole Precursor (A-4)>
According to Synthesis Example 3, BAHF (32.96 g, 0.090 mol), PBOM (29.38 g, 0.082 mol), RT-1000 (10.00 g, 0.010 mol), 1,3-bis ( 3-Aminopropyl) tetramethyldisiloxane (1.49 g, 0.0060 mol), 5-norbornen-2,3-dicarboxylic acid anhydride (5.91 g, 0.036 mol), HFHA (0.60 g, 0) .0010 mol), ODPA (2.17 g, 0.0070 mol), acetic acid (49.22 g, 0.82 mol), NMP 360 g in the same manner to make a powder of polybenzoxazole precursor (A-4). Obtained.

<Synthesis Example 6 Synthesis of Polyamide-imide Precursor (A-5)>
Under a dry nitrogen stream, 27.5 g (0.10 mol) of anhydrous diphenyl ether tricarboxylic acid chloride was dissolved in 500 g of NMP. Here, 39.30 g (0.065 mol) of the hydroxyl group-containing diamine compound obtained in Synthesis Example 1 and 1.24 g (0.005 mol) of 1,3-bis (3-aminopropyl) tetramethyldisiloxane were added to 50 g of NMP. In addition, the reaction was carried out at 20 ° C. for 1 hour and then at 50 ° C. for 2 hours. Subsequently, RT-1000 (10.00 g, 0.010 mol) containing a propylene oxide and a tetramethylene ether glycol structure was added together with 10 g of NMP, and the mixture was reacted at 50 ° C. for 1 hour. Next, 4.36 g (0.04 mol) of 4-aminophenol as an end-capping agent was added together with 5 g of NMP, and the mixture was reacted at 50 ° C. for 2 hours. Then, a solution of 28.6 g (0.24 mol) of N, N-dimethylformamide dimethylacetal diluted with 50 g of NMP was added dropwise over 10 minutes. After the dropping, the mixture was stirred at 50 ° C. for 3 hours. After the stirring was completed, the solution was cooled to room temperature, and then the solution was poured into 3 L of water to obtain a white precipitate. This precipitate was collected by filtration, washed with water three times, and then dried in a vacuum dryer at 80 ° C. for 24 hours to obtain the desired polyamide-imide precursor (A-5).

[Reference Examples 1 to 15]
10 g of the obtained component (A) (A-1 to 5) was added to 3-(5-(((phenylsulfonyloxy) imino) thiophen-2 (5H) -iriden-2-() as a (B) thermoacid generator. 0.2 g (0.52 mmol) of o-tolyl) propanenitrile (B-1), 0.2 g (0.53 mmol) of SI-200 (B-2), (C) HMOM as a thermal cross-linking agent -TPHAP (C-1) is 2.4 g (4.2 mmol) and MW-100LM (C-2) is 1.0 g (2.6 mmol), and (D) is represented by the following formula as a photosensitive compound. 2.0 g (1.8 mmol) of a photosensitive compound was added, and 20 g of γ-butyrolactone as a solvent was added to prepare a varnish, and these characteristics were measured by the above evaluation method. The obtained results are shown in Table 1.

[Reference Examples 16 to 20]
(B) Varnishes were prepared in the same manner as in Reference Examples 1 to 15 except that a thermal acid generator was not used, and these characteristics were measured by the above evaluation method. The results obtained are shown in Table 1.

[Examples 1 to 8, Comparative Examples 1 to 9]
10 g of the obtained component (A) (A-1 to 5) was added to 3-(5-(((phenylsulfonyloxy) imino) thiophen-2 (5H) -iriden-2-() as a (B) thermoacid generator. 0.2 g (0.52 mmol) of o-tolyl) propanenitrile (B-1), or 0.2 g (0.53 mmol), or 0.5 g (1.3) of SI-200 (B-2). 1. 0.2 g (0.25 mmol), 1.5 g (1.9 mmol), or 5.1 g (0.25 mmol) of 0 g (2.6 mmol) or the thermal cross-linking agent (C-3) represented by the following formula. 6.5 g (1.8 mmol) (D) a photosensitive compound represented by the following formula as a photosensitive compound, and (E) a compound represented by the following formula as an antioxidant (E-1) ) To 0.15 g (0.26 mmol) or (E-2) to 0.15 g (0.27 mmol), and 20 g of γ-butyrolactone as a solvent to prepare a varnish, and these characteristics are evaluated by the above evaluation method. The results obtained are shown in Table 2.

[Comparative Examples 10 to 15]
(B) Prepare varnishes in the same manner as in Comparative Examples 2 and 6 to 9 except that a thermal acid generator is not used (Comparative Examples 10 to 14), or (B) SI-200 (B-2) as a thermal acid generator. ) Was added in the same manner as in Comparative Example 2 except that 1.2 g (3.2 mmol) was added (Comparative Example 15), and these characteristics were measured by the above evaluation method. The results obtained are shown in Table 2.

1 Silicon wafer 2 Al pad 3 Passivation film 4 Insulation film 5 Metal (Cr, Ti, etc.) film 6 Metal wiring (Al, Cu, etc.)
7 Insulation film 8 Barrier metal 9 Scribline 10 Handa bump 11 Encapsulating resin 12 Substrate 13 Insulation film 14 Insulation film 15 Metal (Cr, Ti, etc.) film 16 Metal wiring (Ag, Cu, etc.)
17 Metal wiring (Ag, Cu, etc.)
18 Electrode 19 Encapsulating resin

Claims (16)

(A) Containing one or more selected from polybenzoxazole precursors, polyimide precursors, polyamideimide precursors, and copolymers thereof, which have a structural unit represented by the general formula (1) . An alkali-soluble resin having a benzoxazole precursor structure and an aliphatic group, and
A resin composition containing (B) a thermal acid generator and (E) an antioxidant .
A resin composition in which Y in the general formula (1) has an aliphatic group represented by the following general formula (2).

(In the general formula (1), X and Y each independently represent a 2- to 8-valent organic group having two or more carbon atoms. R ¹ and R ² are independently hydrogen or 1 carbon atom, respectively. Represents an organic group of ~ 20; n represents an integer in the range of 10-100,000; r and s represent an integer in the range of 0-2, p and q represent an integer in the range of 0-4. .)

(In the general formula (2), R ³ to R ⁶ independently represent an alkylene group having 1 to 6 carbon atoms, and R ⁷ to R ¹⁴ independently represent hydrogen, fluorine, or an alkyl group having 1 to 6 carbon atoms, respectively. However, the structures represented in parentheses are different. X, y, and z each independently represent an integer of 0 to 35.) The (B) thermal acid generator is one or more selected from the sulfonic acid ester compound represented by the following general formula (3), the sulfonic acid ester compound represented by the general formula (4), and the onium salt. The resin composition according to claim 1 , which comprises a compound.

(In the general formulas (3) and (4), R ²⁰ to R ²² independently represent an aliphatic group having 1 to 12 carbon atoms or an aromatic group having 4 to 12 carbon atoms, respectively.) The resin composition according to claim 1 or 2 , wherein the thermal decomposition start temperature of the (B) thermal acid generator is 140 ° C. or higher and 220 ° C. or lower. The resin composition according to any one of claims 1 to 3 , further comprising (C) a heat-crosslinking agent and (D) a photosensitive compound. The resin composition according to claim 4 , wherein the (C) heat-crosslinking agent contains a heat-crosslinking agent having a structural unit represented by the general formula (5).

(In the general formula (5), R ²⁴ and R ²⁵ each independently represent a hydrogen atom or a methyl group. R ²³ is a divalent organic group having an alkylene group having 2 or more carbon atoms and is linear. , Branched, and annular.) The resin composition according to any one of claims 1 to 5 , wherein the (E) antioxidant contains a compound represented by the general formula (6).

(In the general formula (6), R ²⁶ represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, R ²⁷ represents an alkylene group having 2 or more carbon atoms, and R ²⁸ represents an alkylene group having 2 or more carbon atoms, O. Indicates a 1- to 4-valent organic group containing at least one of an atom and an N atom. K indicates an integer of 1 to 4). A resin sheet formed from the resin composition according to any one of claims 1 to 6 . A cured film obtained by curing the resin composition according to any one of claims 1 to 6 . A cured film obtained by curing the resin sheet according to claim 7 . The cured membrane according to claim 8 or 9 , wherein the benzoxazole precursor structure has a ring closure ratio of 30% or more to polybenzoxazole. A step of applying the resin composition according to any one of claims 1 to 6 onto a substrate, or laminating the resin sheet according to claim 7 onto a substrate, and drying to form a resin film.
An exposure process that exposes a dried resin film, a development process that develops an exposed resin film,
A method for producing a cured film, which comprises a heat treatment step of heat-treating the developed resin film. The method for producing a cured film according to claim 11 , wherein the heat treatment step of heat-treating the developed resin film includes a step of heat-treating at 140 ° C. or higher and 220 ° C. or lower. An interlayer insulating film or a semiconductor protective film on which the cured film according to any one of claims 8 to 10 is arranged. A semiconductor electronic component or semiconductor device in which the cured film according to any one of claims 8 to 10 is arranged as an interlayer insulating film between rewiring. The semiconductor electronic component or semiconductor device according to claim 14 , wherein the rewiring and the interlayer insulating film are repeatedly arranged in 2 to 10 layers. A semiconductor electronic component or a semiconductor device in which the cured film according to any one of claims 8 to 10 is arranged as an interlayer insulating film of adjacent substrates composed of two or more kinds of materials.

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